CN115744836B - Anode protection acid distributor based on battery principle - Google Patents
Anode protection acid distributor based on battery principle Download PDFInfo
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- CN115744836B CN115744836B CN202211134438.XA CN202211134438A CN115744836B CN 115744836 B CN115744836 B CN 115744836B CN 202211134438 A CN202211134438 A CN 202211134438A CN 115744836 B CN115744836 B CN 115744836B
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- Prior art keywords
- acid
- shell
- potential
- electrolytic tank
- tank
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- 239000002253 acid Substances 0.000 title claims abstract description 67
- 239000003792 electrolyte Substances 0.000 claims abstract description 32
- 239000012528 membrane Substances 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000002347 injection Methods 0.000 claims abstract description 4
- 239000007924 injection Substances 0.000 claims abstract description 4
- 239000010865 sewage Substances 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 45
- 239000010935 stainless steel Substances 0.000 claims description 16
- 229910001220 stainless steel Inorganic materials 0.000 claims description 16
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 14
- 235000010344 sodium nitrate Nutrition 0.000 claims description 7
- 239000004317 sodium nitrate Substances 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract description 7
- 238000009434 installation Methods 0.000 abstract description 6
- 238000012423 maintenance Methods 0.000 abstract description 5
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011900 installation process Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 210000005239 tubule Anatomy 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
An anode protection acid distributor based on a battery principle comprises acid distribution tanks, wherein each acid distribution tank is internally provided with at least one high-potential electrolytic tank, the high-potential electrolytic tank comprises a shell and proton exchange membranes which are hermetically arranged on two sides of the shell to form an outer shell of the electrolytic tank, and the outer shell is filled with inner electrolyte and is provided with an inner silk screen or an inner pore plate; the upper part of the shell is provided with a liquid injection port, and the lower part is provided with a sewage outlet. The invention provides a novel anode protection form, which does not need to be electrically connected to the outside of a tower, does not need to be provided with holes and seals of the tower body and does not need to be externally connected with a constant potential rectifier; the installation, the use and the maintenance of the anode protection acid distributor are greatly simplified, and the anode protection acid distributor has better industrial application effect.
Description
Technical Field
The invention belongs to the technical field of concentrated sulfuric acid separators and anodic protection, and particularly relates to an anodic protection acid separator based on a battery principle.
Background
The anodic protection acid distributor is a concentrated sulfuric acid distribution device applied with anodic protection technology, and the structural form of the anodic protection acid distributor is usually a groove pipe type or a pipe type. In sulfuric acid production, the acid distributor is arranged at the top in the drying tower and the absorption tower, and concentrated sulfuric acid conveyed to the top of the drying tower by the acid pump enters the acid distributor and is dispersed into a plurality of trickles, so that the contact area of the concentrated sulfuric acid and air, sulfur dioxide or sulfur trioxide gas can be remarkably improved, and the absorption efficiency is improved.
The anode protection technology is an anti-corrosion technology, and the corrosion rate of the acid distributor made of stainless steel materials in concentrated sulfuric acid after anode protection is reduced to less than 0.1mm/a, so that the acid distributor has ideal service life. The implementation of the anode protection technology requires that an anode protection device is additionally arranged on an acid distributor, one to two cathodes are additionally arranged in each acid distributing groove, and a control reference electrode and a monitoring reference electrode are arranged in the acid distributing groove; all the components are required to be electrically connected to the outside of the tower and connected to a potentiostat, and the potentiostat supplies power to the acid distributor and controls the potential of the acid distributor so as to achieve the effect of anodic protection. The anode protection acid distributor has mature technology and good application effect, but because of more installation components, more complex installation process, the tower body needs to be provided with a lead wire and sealed, special personnel are needed to operate and maintain the potentiostat in the operation process. The installation and use are complicated, and the application of the device is limited.
Disclosure of Invention
The invention provides an anode protection acid distributor based on a battery principle, which does not need to be electrically connected to the outside of a tower, does not need to be provided with holes and seals on the tower body and does not need to be externally connected with a constant potential rectifier; the installation, the use and the maintenance of the anode protection acid distributor are greatly simplified, and the anode protection acid distributor has better industrial application effect.
The technical scheme adopted by the invention is as follows:
an anode protection acid distributor based on a battery principle comprises acid distribution tanks, wherein each acid distribution tank is internally provided with at least one high-potential electrolytic tank, the high-potential electrolytic tank comprises a shell and proton exchange membranes which are hermetically arranged on two sides of the shell to form an outer shell of the electrolytic tank, and the outer shell is filled with inner electrolyte and is provided with an inner silk screen or an inner pore plate; the upper part of the shell is provided with a liquid injection port, and the lower part is provided with a sewage outlet.
The ratio of the surface area of the inner silk screen or the inner pore plate to the contact area of the acid separating tank and the concentrated sulfuric acid is 1:20-1:50.
The internal electrolyte consists of 98% sulfuric acid or 93% sulfuric acid, 65% HNO3 and sodium nitrate, and the specific proportion is as follows: volume of sulfuric acid 150 ml: 1-3 ml nitric acid volume: xg sodium nitrate, x is 0.5-3 g, and the material of the inner silk screen or the inner pore plate matched with the inner electrolyte is stainless steel or alloy material.
The invention adds a high potential electrolytic tank in the acid separating tank, and the higher potential of the electrolytic tank and the low power of the acid separating device body form a potential difference, thereby forming directional current, leading the potential of the acid separating device body to rise and achieving the effect of anode protection. Based on the problem that the current anodic protection acid distributor is complex to install and use, the invention provides a novel anodic protection form, which does not need to be electrically connected to the outside of a tower, does not need to be perforated and sealed, and does not need to be externally connected with a potentiostat; the installation, the use and the maintenance of the anode protection acid distributor are greatly simplified, and the anode protection acid distributor has better industrial application effect. And the acid distributor does not need to be operated and maintained in the use process, and only the inner electrolyte of the high-potential electrolytic tank needs to be replaced periodically, and the replacement period is 12 months.
Drawings
FIG. 1 is a schematic diagram of the overall structure of the present invention;
FIG. 2 is a schematic diagram of the structure of the high potential electrolytic cell of the present invention.
Detailed Description
For a further understanding and appreciation of the various aspects of the invention, reference should be made to the following detailed description of the invention taken in conjunction with the accompanying drawings.
As shown in fig. 1, after the acid distributor is installed in the tower, the high-potential electrolytic tank shown in fig. 2 is fixedly installed in the acid distributor, and the high-potential electrolytic tank is welded with the acid distributor 2 by using a connecting steel bar 5, and one to two high-potential electrolytic tanks are installed in each acid distributor 2; one high potential electrolytic tank is arranged in the middle of the length direction of the acid separating tank, and the two high potential electrolytic tanks are evenly distributed along the length direction of the acid separating tank.
When the acid pump is started, concentrated sulfuric acid enters the acid inlet pipe 1 and then enters the acid separating tank 2, the concentrated sulfuric acid is dispersed to each acid separating tank 2 by means of the communication pipe 3, and a certain depth is kept in the acid separating tank 2, so that the high-potential electrode tank is immersed. The concentrated sulfuric acid flows out from the acid separating tubule 6, and the concentrated sulfuric acid is dispersed into a plurality of thin streams. Plays a role in distributing sulfuric acid and increasing the contact area of concentrated sulfuric acid and gas.
As shown in fig. 2, at least one high-potential electrolytic tank 4 is arranged in each acid separating tank 2, the high-potential electrolytic tank 4 comprises a shell 41 and proton exchange membranes 44 which are arranged on two sides of the shell in a sealing way to form 4 parts of shells of the electrolytic tank, and the shells are filled with an inner electrolyte 42 and are provided with an inner wire mesh or an inner pore plate 43; the upper part of the shell is provided with a liquid injection port 45, and the lower part is provided with a sewage discharge port 46.
The ratio of the surface area of the inner wire mesh or the inner hole plate 43 to the contact area of the acid separation tank 2 and the concentrated sulfuric acid is 1:20-1:50. The ratio shows that 1 unit area of the inner silk screen or the pore plate can protect 20-50 unit areas of the acid distributor, and the smaller the area of the inner silk screen or the inner pore plate is, the better the performance of the high-potential electrolytic tank is. The inner silk screen area is too small to effectively raise the potential of the acid separator, i.e. the protection state cannot be achieved. The inner wire mesh area is too large to be installed in the high-potential electrolytic tank.
When the inner electrolyte is required to be replaced, the drain 46 is opened to drain the liquid in the electrolytic tank; the internal electrolyte is refilled through the filling port 45.
The principle of the invention is explained as follows:
304. the 304L, 316L stainless steel is used for manufacturing a concentrated sulfuric acid dispenser, when anode protection is not applied, the potential of the acid dispenser under the working condition (93% sulfuric acid or 98% sulfuric acid, 60-80 ℃) is E approximately equal to-500 mv (relative to a saturated calomel electrode), the potential is the corrosion potential of the stainless steel, the corrosion rate is higher than 0.5-1.2 mm/a, after anode protection is applied, the potential of the acid dispenser is raised to 100-300 mv even if a potentiostat is used for supplying positive direct current to the acid dispenser, the passivation potential of the stainless steel is entered, the corrosion rate of the stainless steel is obviously reduced, the corrosion rate is less than 0.1mm/a, and the service life of the acid dispenser is greatly prolonged.
In the invention, a high-potential electrolytic tank is used for supplying power to the acid distributor, and an inner wire mesh or an inner hole plate is made of stainless steel or alloy material and has high specific surface area, and is soaked in an inner electrolyte; the electrolyte adopts oxidizing inorganic acid and other components, and the concentration and components of the inner electrolyte can be adjusted according to the required potential, so that the inner wire mesh or the inner hole plate forms higher potential in the inner electrolyte.
The inner electrolyte 42 in the invention is prepared from 98 percent sulfuric acid or 93 percent sulfuric acid and 65 percent HNO 3 And sodium nitrate, the specific proportion is: volume of sulfuric acid 150 ml: 1-3 ml nitric acid volume: xg sodium nitrate, x is 0.5-3 g, and the inner silk screen or inner pore plate 43 matched with the inner electrolyte is made of stainless steel or alloy materials, such as titanium materials, 254SMO, 310S, 2507 and the like.
The process and verification data for determining the concentration and the components of the internal electrolyte in the invention are as follows:
the verification process is that the H-type electrolytic cell is immersed in 1cm by adding 150ml of sulfuric acid plus 1.5g of sodium nitrate to the left side 2 310s stainless steel of (2); adding 150ml sulfuric acid on the right side, soaking in 20cm 2 310s stainless steel of (c). The initial potential of the left stainless steel is about 400mv, the initial potential of the right stainless steel is-450 mv, the left stainless steel and the right stainless steel are short-circuited by a wire, the potential of the right stainless steel is quickly increased to 220mv, then is slowly increased to 360mv after reaching 310mv for 24 hours, the potential is continuously maintained, after 7X 24 hours of experiments, the right test piece is taken out and weighed, the calculated corrosion rate is about 0.03mm/a, and the right test piece is well protected.
The composition of the inner electrolyte is regulated, so that the potential of the inner wire mesh or the inner hole plate in the inner electrolyte is more than 400mv, and the test results of the regulating composition are shown in the following table:
the proton exchange membrane is arranged at two ends of the high-potential electrolytic tank in a sealing way, plays a role in isolating inner electrolyte and outer electrolyte, the inner electrolyte and the outer electrolyte can carry out proton exchange and electron transfer, but the inner electrolyte and the outer electrolyte cannot carry out substance exchange, and the components and the concentration of the inner electrolyte and the outer electrolyte are basically kept constant; the shell of the electrolytic tank is filled with electrolyte, and the shell is connected with the acid separating tank through a connecting steel bar 5, so that the electrolytic tank is electrically connected with the acid separating tank.
After the high potential electrolytic tank is communicated with the acid separating tank, the potential E of the inner wire mesh or the inner hole plate Inner part And acid separator potential E Dividing into The potential difference exists to enable the electron migration to generate current with the current magnitude of I= (E) Inner part -E Dividing into ）/（R Solution +R Film and method for producing the same + R Membrane boundary +R Dividing into ），R Solution Solution resistance as electrode migration path, R Film and method for producing the same Is proton exchange membrane internal resistance, R Membrane boundary Is the interface resistance of the proton exchange membrane and the inner electrolyte and the outer electrolyte, R Dividing into Is the interface resistance of the acid separating tank contacted with the concentrated sulfuric acid. The electric potential of the acid distributor is gradually increased to passivation potential by the current, and the same protection effect is achieved, namely, the corrosion rate is less than 0.1mm/a.
The high-potential electrolytic tank is used for replacing an external constant potential instrument, an external power supply is not required, the acid distributor in the tower is not required to be electrically connected to the outside of the tower, the tower body is not required to be provided with holes, and the installation can be completed in the tower. No special personnel are required for maintenance and instrument operation, and only maintenance is required during the device parking period. The inner electrolyte of the high potential electrolytic tank can be replaced, and the concentration and the composition can be adjusted according to the required potential.
Claims (1)
1. An anodic protection acid distributor based on a battery principle comprises acid distribution tanks and is characterized in that each acid distribution tank (2) is internally provided with at least one high-potential electrolytic tank (4), the high-potential electrolytic tank (4) comprises a shell (41) and proton exchange membranes (44) which are hermetically arranged at two sides of the shell to form the shell of the electrolytic tank (4), and the shell is filled with an inner electrolyte (42) and is provided with an inner silk screen or an inner pore plate (43); the upper part of the shell is provided with a liquid injection port (45), and the lower part is provided with a sewage outlet (46); the ratio of the surface area of the inner silk screen or the inner hole plate (43) to the contact area of the acid separating tank (2) and the concentrated sulfuric acid is 1:20-1:50; the inner electrolyte (42) consists of 98% sulfuric acid or 93% sulfuric acid, 65% HNO3 and sodium nitrate, and the specific proportion is as follows: volume of sulfuric acid 150 ml: 1-3 ml nitric acid volume: xg sodium nitrate, x is 0.5-3 g, and the inner wire mesh or the inner hole plate (43) matched with the inner electrolyte is made of stainless steel or alloy material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211134438.XA CN115744836B (en) | 2022-09-19 | 2022-09-19 | Anode protection acid distributor based on battery principle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211134438.XA CN115744836B (en) | 2022-09-19 | 2022-09-19 | Anode protection acid distributor based on battery principle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115744836A CN115744836A (en) | 2023-03-07 |
| CN115744836B true CN115744836B (en) | 2024-02-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211134438.XA Active CN115744836B (en) | 2022-09-19 | 2022-09-19 | Anode protection acid distributor based on battery principle |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1400036A (en) * | 2001-08-05 | 2003-03-05 | 天华化工机械及自动化研究设计院 | Anode protective acid spreader |
| CN1408900A (en) * | 2001-09-20 | 2003-04-09 | 兰州兴业材料保护有限公司 | Anode protection anticorrosion method for acid separating device |
| CN201809167U (en) * | 2010-01-26 | 2011-04-27 | 南京高源环保工程有限公司 | Trough-pipe type acid distributor with anodic protection |
| CN107109672A (en) * | 2014-09-15 | 2017-08-29 | 卡勒拉公司 | Use the electro-chemical systems and method of metal halide formation product |
| CN214622435U (en) * | 2021-03-03 | 2021-11-05 | 天华化工机械及自动化研究设计院有限公司 | Integral reference electrode mounting structure |
-
2022
- 2022-09-19 CN CN202211134438.XA patent/CN115744836B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1400036A (en) * | 2001-08-05 | 2003-03-05 | 天华化工机械及自动化研究设计院 | Anode protective acid spreader |
| CN1408900A (en) * | 2001-09-20 | 2003-04-09 | 兰州兴业材料保护有限公司 | Anode protection anticorrosion method for acid separating device |
| CN201809167U (en) * | 2010-01-26 | 2011-04-27 | 南京高源环保工程有限公司 | Trough-pipe type acid distributor with anodic protection |
| CN107109672A (en) * | 2014-09-15 | 2017-08-29 | 卡勒拉公司 | Use the electro-chemical systems and method of metal halide formation product |
| CN214622435U (en) * | 2021-03-03 | 2021-11-05 | 天华化工机械及自动化研究设计院有限公司 | Integral reference electrode mounting structure |
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| Publication number | Publication date |
|---|---|
| CN115744836A (en) | 2023-03-07 |
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